Dyestuffs of the dioxazine series



United States Patent 71 J 2.693.461

emit d Nov. .2, 954

2 693467 7 iv for example; under superatmospheric pressure at atemperature within the range of l200 C. The reduc- DYESTUFFS OF THEDIOXAZINE SERIES tion of the nitro glroulp can be ciarried out in knownmanner, or examp e, y means 0 iron. Walter Andemu Bummgen and Karl SeltzBasel Swlt' 5 The condensation of the resulting 2-cycloalkylaminoi'asslgnors to Basel swtzefland S-amino-l-sulfonic acid of the formula (4)containing a SWISS firm a further substituent as aforesaid with 2:3 :5:6-tetrachlo- N Drawing, A li ti M 4, 1953, roquinone is likewisecarried out with advantage in an S i l N 352,964 aqueousdmedium wliththelacllldition 03 an acidzbmdng e 0 C P i y, application SwitzerlandMay 17,1952 Zfifigflfjffiiflf False tempera 4C1 i (C1, 260-446) Thetreatment of the resulting compounds of the H formula (3) with an agentcapable of bringing about The present invention provides new dyestufis'of the ring closure may be carriedout in a manner in itself dioxazineseries which, for example,like the dyestuft of 5 known with the use ofan agent capable of bringing about the formula ring closure which byvirtue of'its oxidizing action 18 1 01 X i v N l O 0111-05, X- NH-C on,GET-CH2 on cn HN x CHFOH CHz-(l 1 23 1 (in which one of the twosubstituents X bound to the 25 capable of converting quinones having theatomic groupsame benzene nucleus is a sulfonic acid group and e mg Iother a chlorine atom) correspond to the general formula 2 I 01 If i N oi X- NH-R R-EN- X 0 N into the corresponding dioxazines having the atomc X in as gmuPing I in which R represents a cycloalkyl radical, and oneof the two substituents X bound to the same benzene nucleus represents asulfonic acid group and the other a substituent incapable of saltformation. a 40 i The new dyestuffs of the formula (2) are made inaccordance with the invention by treating with an agent.

capable of bringing about ring closure a compound of Espiiclany Sultableq E Purpose 1S \Smfunc .acld

the formula g taining free sulfur trioxide (oleum); the content ofsulfur trloxide in the oleum may vary within wide limits e. g. from 5-65per cent. Good results are generally /NH\ /0 obtained with an oleumcontaining about 5 to 24 per cent. X NHR of free sulfur trioxide. Ringclosure with \the use of oleum may be carried out, for example, at atemperature o HN X of 10-25 C., or there may be required, for example,tem- OsH 1 peratures up to about 90 C- If desired, the oleum may bereplaced wholly or in part by chlorosulfonic acid.

The dioxazine may be isolated from the acid reaction in which Rrepresents a cycloalkyl radical and X r pmixture advantageously bydiluting the mixture with resents a substituent incapable of saltformation. water or pouring it onto ice, and filtering ad the pre- Thecompounds of the formula (3) se'ring as starting cipitated dyestuff. Thedyestufi may be purified by dismaterials can be obtained by condensingone mol of solution in Water with the addition of an alkali, for exam-2:325:6-tetrachloroquinone (chloraml) with 2 mols of a ple, an alkalicarbonate, if desired, filtering the solution, compound of the formulaand salting out the dyestu The dyestutf is then con- (4) vertcd into analkali salt such as is well suited for dyeing. X- NH2 As compared withother direct-dyeing dyestufis of the dioxazine series the products ofthis invention have the advantage, on the one hand, that ring closurecan be brought about in a very simple manner and, on the other, 0 E thatdyestufis having a good afii 'ty for cellulose fibers are a obtaineddirectly, that is tosay, without the subsequent in which R and X havethe meaning already given. The partial splitting off of sulfonicacidgroups.

compounds of the formula (4) in which R represents a The new dyestufisof the above formula (2) are suitcyclohexyl radical, and X represents ahalogen atom, for able for dyeing and printing a very wide variety ofexample, a bromine a m ospoolally a Chlorine om, materials, for example,those of animal origin such as are particularly valuable. leather, silkand wool, or artificial fibers of casein, or of The Compounds of theformula are advantageously superpolyamides or superpolyurethanes. Asstated above, prepared by condensing an alkali salt of a Z-halogentheyhave an especially good affinity forcellulose-connitrobenzene-l-sulfonic acid, which contains in the 3taining materials such as paper, linen, cotton and maposition asubstitutent incapable of salt formation, for terials consisting ofregenerated cellulose such as artiexample an alkali salt of 2:3dichloro5nitro-l-sulfonic ficial silk, staple fibers or foils ofregenerated cellulose. acid or 2:3-dibromo-5-nitrobenzene-l-sulfonicacid, with The dyeings produced on cellulose-containing materials acycloalkylamine, and reducing the nitro group in the with the newdyestufis are distinguished by the high purity product so obtained to.an amino group. The condensaof their tints, which are usually reddishblue, and also tion is advantageously carried out in an aqueous mediumby their good fastness' to light. In general the fastness with theaddition of an acid-binding agent, such, for 0 to light of the dyeingsremains substantially unimpaired example, as magnesium oxide, -ataraisedtemperature, by the usual treatments w1thanti-creasing agents.

3 4 The following examples illustrate the invention, the Example 3 Partsand Percentages being by ht: 100 pints of cotton are entered at 50 C.into 2. Example 1 dyebath which contains in 3000 parts of water 1 partof the dyestuff obtainable as described in the first paragraph grams ofthe compound of the formula 5 of Example 1. The temperature is raised to90 C. in

01 SOaNtt NH O CHz-CEz o1 NHCH CH2 CH2CH2 T Cl CHE-CH: CH; CH H1\ \HN/CHr-OHz SOKNE I are dissolved in 200 parts of oleum of 24 per cent. thecourse of /2 hour, and 30 parts of crystalline sodium strength, and thewhole is heated for one hour at 90-95 sulfate are added. The dyeing isthen carried on for C., while stirring. The deep blue solution is thenpoured one hour at 90-95 C. and there is obtained a pure on to 700 partsof ice, and the precipitated dyestuif reddish blue dyeing of very goodfastness to light. is filtered 01f. The dyestufi is stirred in 300 partsof What is claimed is:

water, the solution is rendered neutral with sodium car- 1. A dyestulfof the dioxazine series which correbonate or another alkali, and thedyestutf is completely sponds to the formula precipitated by means of 60parts of sodium chloride.

The product is then filtered off and dried.

i r The dyestuif is a dark powder which dissolves in water with a violetcoloration, and dyes cotton, artificial silk of regenerated celluloseand paper pure reddish blue I \0 \N/ tints having a very good fastnessto light.

The compound of the above formula is prepared by heating 147 parts ofsodium 5-nitro-2:3-dich1oro-1-sulfonate vn'th 52 parts ofcyclohexylamine and 11 parts in which R represents a cyclohexyl radical,and one of of magnesium oxide in 600 parts of water for 5 hours the twosubstituents Xbound to the same benzene nucleus at 160-165 C. in anautoclave, and the condensation represents a sulfonic acid group and theother a halogen product is then reduced in the usual manner with ironatom.

to yield 2-cyclohexylamino-3-chloro-5-aminobenzene-1- 2. A dyestuff ofthe dioxazine series which corresulfonic acid. sponds to the formula 01X N 0 I CH2CH2 X- NHOH oH, CHg CHz on CH EN 2: Clix-OH CH2CH2 X I 60.9parts of the above amine, 24.6 parts of chloranil in which one of thetwo substituents X bound to the and 9.3 parts of magnesium oxide arestirred in 300 same benzene nucleus represents a sulfonic acid groupparts of water for 6 hours at 6S C. The precipitated and the otherrepresents a member selected from the condensation product is thenfiltered oif, washed with group consisting of a bromine and a chlorineatom. water until the filtrate becomes colorless, and dried 50 3. Adyestuif of the dioxazine series which correin vacuo at -80 C. m spondsto the formula 01 X N i O i /CHzC -1f: x NH-OH OH: CH2CH2 CHz-CH: CH2CHHN X CHz-C- h l I X C] Example 2 in which one of the two substituentsX bound to the A dyestufl. similar to that described in Example 1 i samebenzene nucleus represents a sulfomc acid group obtained by treating thecompound of the formula and the other represents a bfomlne atom- 01SOaNa I NH I 0 /CH2C1\12 Bri NHCH CH2 CH2CH2 OHz-CH; 0H2 OH-HN BrCHz-CH2 SO3N3 C] with oleum of 24 per cent. strength. The starting 4. Adyestufi of the dioxazine series which corrematerial is prepared bycondensing 1 mol of chloranil sponds to the formula 01 X N O I CHz-CH:X- -NH-0 on, CHz-CHz CHg-CH: 0H2 CH-HN O \N/ X CH2CH:

X 01 with 2 mols of sodium 2-cyclohexylamino-3-bromo-5 in which one ofthe two substituents X bound to the same aminobenzene-l-sulfonate, whichhas been obtained by benzene nucleus represents a sulfonic acid groupand condensing cyclohexylamine with 5-nitro-2:3-dibrom0 the otherrepresents a chlorine atom.

benzene-l-sulfonic acid or with5-nitro-2-chloro-3-bromobenzene-l-sulfonic acid, and subsequentlyreducing with iron the product so obtained.

N 0' references cited.

1. A DYESTUFF OF THE DIOXINE SERIES WHICH CORRESPONDS TO THE FORMULA